DE10259672A1 - Process for the preparation of alkoxycarbonylamino-triazines - Google Patents

Abstract

In a process for preparing alkoxycarbonylaminotriazines, di- or triaminotriazines are reacted with cyclic carbonic esters and optionally with minor amounts of acyclic carbonic esters in the presence of an alcohol and of an alkali metal alkoxide or alkaline earth metal alkoxide as a base.

Description

The present invention relates to a new process for the production of alkoxycarbonylamino-triazines by reacting di- or triaminotriazines with cyclic carbonic acid esters and optionally with minor amounts of acyclic carbonic acid esters in the presence of an alkanol and an alkali or alkaline earth alkoxide as a base.

From the EP-A-624 577 the production of alkoxycarbonylaminotriazines by reacting triazines, for example melamine, with acyclic carbonic acid esters in the presence of a base is known. As a rule, melamine is reacted there as a base with a carbonic acid ester, for example dimethyl carbonate, in the presence of the alkanol on which the carbonic acid ester is based, here for example methanol, and in the presence of an alkali alkanolate based on the alkanol on which the carbonic acid ester is based, here for example methanol. It is also described to react melamine, for example with dimethyl carbonate, in the presence of a higher alcohol, for example butanol or 2-ethylhexanol, and the corresponding sodium alkanolate, here for example sodium butanolate or sodium (2-ethylhexanolate) as the base.

The expert is in the EP-A-624 577 the teaching conveys that the process described there can only be carried out with acyclic carbonic acid esters.

Object of the present invention it was now a new process for the production of alkoxycarbonylamino-triazines to provide, which is easy to do and the manufacture of a wide range of mixtures of mixed functionalized and / or isomeric Alkoxycarbonylamino-triazines in high yield and purity the industrially easily accessible cyclic carbonic acid ester allowed.

in der
Y¹ Wasserstoff, C₁-C₄-Alkyl, gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenyl oder einen Rest der Formel NR⁵R⁶ und
R¹, R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander jeweils Wasserstoff oder einen Rest der Formel COOX oder X, worin X für C₁-C₁₃-Alkyl, dessen Kohlenstoffgerüst durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen und/oder durch Hydroxy substituiert sein kann, oder C₃-C₆-Alkenyl steht, bedeuten,
mit der Maßgabe, dass in Formel I mindestens einer der Reste R¹ bis R⁴, oder wenn Y¹ für NR⁵R⁶ steht, mindestens einer der Reste R¹ bis R⁶ COOX bedeutet,
durch Umsetzung eines Triazins der Formel II

in der
Y² Wasserstoff, C₁-C₄-Alkyl, Amino oder gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenyl bedeutet, und
R¹ bis R⁴ jeweils die obengenannte Bedeutung besitzen,
mit der Maßgabe, dass in Formel II, wenn Y² nicht für Amino steht, mindestens einer der Reste R¹ bis R⁴ Wasserstoff bedeutet, mit Kohlensäureestern in Gegenwart eines Alkohols und einer Base vorteilhaft gelingt, wenn man das Triazin der Formel II mit einem cyclischen Kohlensäureester der Formel III

in der
L Ethylen, 1,2- oder 1,3-Propylen oder 1,2-, 1,4- 2,3-, oder 1,3-Butylen bedeutet,
sowie gegebenenfalls mit untergeordneten Mengen eines acyclischen Kohlensäureesters der Formel IV Z¹O-CO-OZ² (IV), in der
Z¹ und Z² unabhängig voneinander jeweils C₁-C₈-Alkyl bedeuten, und einem C₁-C₁₃-Alkanol, dessen Kohlenstoffgerüst durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen und/oder durch Hydroxy substituiert sein kann, oder einem C₃-C₆-Alkenol in Gegenwart eines Alkali- oder Erdalkalialkanolats als Base umsetzt.It has now been found that the preparation of alkoxycarbonylamino-triazines of the formula I

in the
Y ^{1 is} hydrogen, C ₁ -C ₄ alkyl, phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen or a radical of the formula NR ⁵ R ⁶ and
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently of one another are hydrogen or a radical of the formula COOX or X, where X is C ₁ -C ₁₃ -alkyl, the carbon skeleton of which has 1 or 2 oxygen atoms in ether function can be interrupted and / or substituted by hydroxy, or is C ₃ -C ₆ alkenyl,
with the proviso that in formula I at least one of the radicals R ¹ to R ⁴ , or when Y ^{1 is} NR ⁵ R ⁶ , at least one of the radicals R ¹ to R ^{6 is} COOX,
by reacting a triazine of the formula II

in the
Y ^{2 is} hydrogen, C ₁ -C ₄ alkyl, amino or phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen, and
R ¹ to R ⁴ each have the meaning given above,
with the proviso that in formula II, if Y ^{2 is} not amino, at least one of the radicals R ¹ to R ^{4 is} hydrogen, with carbonic acid esters in the presence of an alcohol and a base, the triazine of the formula II can be advantageously obtained with a cyclic carbonic acid ester of formula III

in the
L is ethylene, 1,2- or 1,3-propylene or 1,2-, 1,4-2,3- or 1,3-butylene,
and optionally with minor amounts of an acyclic carbonic acid ester of the formula IV Z ¹ O-CO-OZ ² (IV), in the
Z ¹ and Z ² each independently represent C ₁ -C ₈ alkyl, and a C ₁ -C ₁₃ alkanol, the carbon skeleton of which can be interrupted by 1 or 2 oxygen atoms in ether function and / or substituted by hydroxy, or a C ₃ -C ₆ -alkenol in the presence of an alkali or alkaline earth alkoxide as a base.

All in the formulas listed here contained alkyl residues can be both straight and branched.

Residues Y ¹ , Y ² , X, Z ¹ and Z ² are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

X, Z ¹ and Z ² are, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl and isooctyl.

Residues X are still e.g. nonyl, Isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,7-dioxaoctyl, 4,7-dioxaoctyl, 2- or 3-butoxypropyl or 2-4-butoxybutyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 3-hydroxybut-2-yl, Allyl, methallyl, ethallyl, 2-, 3- or 4-penten-1-yl or 2-, 3-, 4- or 5-hexen-1-yl. (The above terms isooctyl, isononyl, Isodecyl and isotridecyl are trivial names and come from the alcohols obtained after the oxo synthesis - cf. in addition Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 1, pages 290 to 293, as well as vol. A 10, pages 284 and 285.)

Residues Y ¹ and Y ² are furthermore, for example, phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-fluorophenyl or 2-, 3- or 4-chlorophenyl.

Suitable alkanols in the process according to the invention can be used, are, for example, methanol, ethanol, propanol, isopropanol, butanol, Isobutanol, sec-butanol, tert-butanol, Pentanol, isopentanol, neopentanol, tert-pentanol, hexanol, 2-methylpentanol, Heptanol, octanol, 2-ethylhexanol, isooctanol, nonanol, isononanol, Decanol, isodecanol, undecanol, dodecanol, tridecanol, isotridecanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2- or 3-methoxypropanol, 2- or 3-ethoxypropanol, 2- or 3-propoxypropanol, 2- or 4-methoxybutanol, 2- or 4-ethoxybutanol, 3,6-dioxaheptanol, 3,6-dioxaoctanol, 3,7-dioxaoctanol, 4,7-dioxaoctanol, 2- or 3-Butoxypropanol or 2- or 4-Butoxybutanol to name.

Suitable C ₃ -C ₆ alkenols which can be used in the process according to the invention are, for example, allyl alcohol, methallyl alcohol, ethallyl alcohol, 2-, 3- or 4-penten-1-ol or 2-, 3-, 4- or 5 hexene-1-ol.

The use of C ₁ -C ₁₃ alkanols is preferred, the use of C ₁ -C ₇ alkanols being particularly noteworthy.

The in the inventive method alcohols used can either individually or as mixtures with one another reach. In the latter case, you can the number of mixing partners and the mixing ratios be arbitrary.

If subsequently alkanol or alkanolate mentioned , these terms also include the alkenols mentioned above or alkenolates.

Suitable alkali or alkaline earth alkanolates, the use according to the invention can get are e.g. the lithium, sodium, potassium, magnesium or calcium salts the closer above designated alkanols. The use of alkali methanolates, in particular of sodium methoxide is preferred.

Alkali or alkaline earth alkoxide can either in a solid state or in dissolved or suspended form apply.

Preferred solvents / diluents in this case are in particular the alcohols specified above, alone or as a mixture with each other. However, others can also known and usual inert diluent apply.

A procedure using a catalyst is also possible.

For example, phase transfer catalysts the way they e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 19, pages 239 to 248.

Other catalysts can be metal salts or complexes, preferably oxides, chalcogenates, carbonates or halides of alkali, alkaline earth or transition metals. To call here are in particular lithium chloride, magnesium chloride, for example or sodium carbonate.

In the process according to the invention come per mole equivalent Amino groups in the triazine of the formula II generally 1 to 50 mol, preferably 3 to 30 mol, alkanol for use.

Furthermore, come in the inventive method per mole equivalent Amino groups in the triazine of the formula II generally 0.1 to 10 mol, preferably 1 to 3 mol, cyclic carbonic acid ester of the formula III for use.

Furthermore, come in the inventive method per mole equivalent Amino groups in the triazine of the formula II generally 0.1 to 10 mol, preferably 1 to 7 mol equivalent, Alkali or alkaline earth alkoxide for use.

If the process according to the invention is carried out in the presence of a catalyst, generally ^10-10 to 10% by weight, preferably ^10-3 to 1% by weight, of catalyst, based in each case on the weight of the triazine of the formula II, are used ,

The process according to the invention is general at a temperature of 20 to 180 ° C, preferably 50 to 100 ° C, performed.

One usually works under atmospheric Pressure, however, the application of increased pressure, usually until to 8 bar, possible is.

The inventive method is cyclic Kohlensäureestern of formula III and optionally with minor amounts acyclic carbonic acid esters carried out. Subordinate amounts in the sense of the invention means that up to to 30 mol% of the cyclic carbonic acid esters of the formula III acyclic carbonic acid esters Formula IV can be replaced.

A procedure is preferred in the 0 to 25 mol%, preferably 0 to 10 mol% of the cyclic carbonic acid esters of formula III replaced by acyclic carbonic acid esters of formula IV could be.

If acyclic carbonic acid esters of the formula IV are also used in the process according to the invention, preference is given to those in which Z ¹ and Z ² independently of one another are each C ₁ -C ₄ -alkyl.

Of particular interest is the use of triazines of the formula II in which Y ^{2 is} amino as starting material in the process according to the invention, the use of melamine (2,4,6-triamino-1,3,5-triazine) being particularly emphasized ,

Of particular interest is still the use of a cyclic carbonic acid ester of the formula III, in the L means ethylene or 1,2-propylene, especially ethylene.

in derThe production of alkoxycarbonylamino-triazines of the formula V is of very special interest

in the

R ¹ to R ⁶ each have the abovementioned meaning, with the proviso that three of these radicals each represent hydrogen and the remaining three of these radicals each represent a radical of the formula COOX, in which X has the abovementioned meaning, by means of the process according to the invention.

The preparation of the alkoxycarbonylamino-triazines according to the invention can be done in different variants (A-F).

The method according to the invention is advantageous done so that you put triazine II and alkanol and then in any order Alkali or alkaline earth alkoxide, in the solid state and / or dissolved in alkanol, and carbonic acid esters metered in, the metering of alkali or alkaline earth alkoxide and carbonic acid esters Completely before the start of the reaction or partly before the start of the reaction and partly can take place after the start of the reaction. By distilling certain Amounts of alkanol from the reaction mixture before and / or during the Reaction can be the setting of desired alkanol ratios cause.

In variant A) triazine II, alkanol and the dissolved Combined alkali or alkaline earth alkoxide and then at increased Temperature (usually 30 to 85 ° C) carbonic acid added.

In variant B) all components submitted before the start of the reaction.

In variant C) triazine II, Alkanol and carbonic acid esters submitted and part of the alkali or alkaline earth metal alkoxide, the partly in dissolved and partly in the solid state, before the start of the reaction and Remainder added after the start of the reaction.

In variant D) triazine II, Alkanol and carbonic acid esters submitted and part of the alkali or alkaline earth metal alkoxide, the either in dissolved Form or in a solid state, before the start of the reaction and Remainder added after the start of the reaction.

In variant E) before or during the Reaction catalysts added.

In variant F) are before or during the Different alkali alkanolates added to the reaction (e.g. lithium alkoxide and sodium alkanolate).

The reaction can also be carried out that melamine while the reaction is metered in gradually or continuously.

The process according to the invention can be carried out in a conventional manner Reaction apparatus, e.g. a boiler or tubular reactor. If one carries out the new process so that the molar ratio triazine of formula II: alkanol if possible is high, the use is apparatus with a mixing effect at highly viscous or inhomogeneous reaction mixtures, e.g. Kneading reactors, preferred. Also the use of self-cleaning devices with a mixing effect is possible. Such apparatuses are known per se and are commercially available. Suitable reactors of this type are e.g. the chamber reactor, the circulation reactor or the screw reactor.

The processing is advantageous the resulting reaction mixture in the absence of additional solvent instead of.

To do this, the alkanolic reaction mixture directly with acid, either by adding acid or by transferring the Reaction mixture in a suitable acid, contacted.

The acid can be concentrated be added, and the addition of water during or after the metering the acid respectively. Especially when using aqueous or highly concentrated acids must during suitable mixing can be guaranteed for the dosage. To acidify the Reaction mixture can all usual and industrially available organic and inorganic acids in any concentration, preferably 30 to 85% by weight aqueous Solutions, be used. Mineral acids whose Salts high water solubility have, such as nitric acid, sulfuric acid or phosphoric acid, but also the carboxylic acid formic acid should be mentioned here.

After adding acid to the Reaction mixture form an aqueous, also the diols Formula containing HO-L-OH, in which L has the meaning given above Phase and an alkanolic phase, which are separated from each other. The separation of the phases is temperature and pH dependent, see above that the addition of additional Water at a temperature of 10 to 70 ° C, preferably from 15 to 50 ° C, and at a pH of 0 to 8, preferably from 2 to 5, takes place.

The target products result directly as a 10 to 80% by weight alkanolic solution. By subsequent concentration the alkanolic phase is entrained water z. T. azeotropic (e.g. with butanol) removed, so that further drying steps, e.g. the addition of drying agents are not necessary.

Working up the reaction mixture can of course also after neutralization with any acid by extraction, washing and / or by filtration.

The new process, both in carried out continuously as well as discontinuously can deliver the target products in high yield and purity. Another advantage of the method according to the invention is the use of cyclic carbonic acid esters, the opposite the acyclic carbonic acid esters are considered to be problem-free in terms of safety.

In the case of the method according to the invention available Alkoxycarbonylamino-triazines are valuable raw materials for coatings.

The following examples are intended to Invention closer explain.

All reactions were carried out with exclusion of moisture. In the case of alkylcarbonylamino-triazine mixtures, the individual components could be determined by HPLC (20 μl loop; W detector (250 nm); 1 ml / min, acetonitrile: aqueous potassium dihydrogen phosphate (0.05 mol / 1) = 1: 1 ; Separate column Purospher-RP18e). The quantities of the components in the following examples are given in area percent (A .-%). The substance was identified by high-resolution mass spectrometry, partly in the form of a direct HPLC-MS coupling or by means of ¹ H and ¹³ C nuclear magnetic resonance spectroscopy.

example 1

31.5 g (0.25 mol) of melamine, 1200 ml of butanol, 88.1 g (1 mol) of ethylene carbonate and 94.5 g (1.75 mol) of sodium methoxide (solid) were initially charged at a temperature of 20.degree. The reaction mixture was then heated to approximately 70 ° C. and stirred at approximately 70 ° C. for a further 120 minutes. After the mixture has cooled down At about 30 ° C., 367.6 g (1.75 mol) of aqueous nitric acid (30% by weight) were added with stirring. The aqueous phase was separated and the organic homogeneous phase was washed a further 3 times with 300 ml of water each time. Concentration of the organic phase resulted in a 50% by weight butanolic product solution, the predominant 2,4,6-tris (butoxycarbonylamino) -1,3,5-triazine (30.2 A%), 2-methoxycarbonylamino-4 , 6-bis (butoxycarbonylamino) -1,3,5-triazine (35.5 A%), 2,4-bis (butoxycarbonylamino) -6-amino-1,3,5-triazine (7.3 A- %), 2,4-bis (methoxycarbonylamino) -6-butoxycarbonylamino-1,3,5-triazine (12.1 A%), 2-butoxycarbonylamino-4-methoxycarbonylamino-6-amino-1,3,5- triazine (5.9 A%) and tris (methoxycarbonylamino) -1,3,5-triazine (4 A%) contained (HPLC, ¹ H, ¹³ C NMR).

Example 2

Example 2 became analogous to Example 1 performed, however, the reaction temperature was 75 ° C. Contained after 120 minutes the reaction mixture predominantly 2,4,6-tris (butoxycarbonylamino) -1,3,5-triazine (33.6 A%), 2-methoxycarbonylamino-4,6-bis (butoxycarbonylamino) -1,3,5-triazine (32.1 A%), 2,4-bis (butoxycarbonylamino) - 6-amino-1,3,5-triazine (9.1 A%), 2,4-bis (methoxycarbonylamino) -6-butoxycarbonylamino-1,3,5-triazine (8.8 A%), 2-butoxycarbonylamino-4-methoxycarbonylamino-6-amino-1,3,5-triazine (5.3 A%) and tris (methoxycarbonylamino) -1,3,5-triazine (4.5 A%)

Example 3

31.5 g (0.25 mol) melamine, 112 ml Butanol, 88.1 g (1 mol) of ethylene carbonate and 151.3 g (1.75 mol) of sodium methoxide (solid) were placed in a kneading reactor (List reactor) at a temperature of 20 ° C. Then was the reaction mixture kneaded at 75 ° C for 1 hour. Through direct analysis the reaction mixture the main components of the mixture identify as 2,4,6-tris (methoxycarbonylamino) - 1,3,5-triazine, 2-butoxycarbonylamino-4,6-bis (methoxycarbonylamino) -1,3,5-triazine and 2,4-bis (butoxycarbonylamino) -6-methoxycarbonylamino-1,3,5-triazine, 2,4,6-tris (butoxycarbonylamino) - 1,3,5-triazine, (HPLC, HPLC-MS).

Example 4

29 g (0.23 mol) of melamine, 976 ml of butanol, 81 g (0.92 mol) of ethylene carbonate and 87 g (1.61 mol) of sodium methoxide (solid) were introduced at a temperature of 20 ° C. The reaction mixture was then heated to approximately 70 ° C. and stirred at approximately 70 ° C. for a further 120 minutes. After the mixture had cooled to about 30 ° C., 338 g (1.61 mol) of aqueous nitric acid (30% by weight) were added with stirring. The aqueous phase was separated and the organic homogeneous phase was washed a further 3 times with 300 ml of water each time. Concentration of the organic phase resulted in a 50% by weight butanolic product solution, the predominant 2,4,6-tris (butoxycarbonylamino) -1,3,5-triazine (29.3 A%), 2-methoxycarbonylamino-4 , 6-bis (butoxycarbonylamino) -1,3,5-triazine (37.5 A%), 2,4-bis (butoxycarbonylamino) - 6-amino-1,3,5-triazine (6.3 A- %), 2,4-bis (methoxycarbonylamino) -6-butoxycarbonylamino-1,3,5-triazine (13.2 A%), 2-butoxycarbonylamino-4-methoxycarbonylamino-6-amino-1,3,5- triazine (5.8 A%) and tris (methoxycarbonylamino) -1,3,5-triazine (4.7 A%) contained (HPLC, ¹ H, ¹³ C NMR).

Example 5

29.0 g (0.23 mol) melamine, 1200 ml butanol, 72.9 g (0.83 mol) ethylene carbonate 8.3 g (0.09 mol) dimethyl carbonate and 87.0 g (1.61 mol) sodium methoxide (solid) were presented at a temperature of 20 ° C. The reaction mixture was then heated to approximately 80 ° C. and stirred at approximately 80 ° C. for a further 120 minutes. After the mixture had cooled to about 30 ° C., 338.2 g (1.61 mol) of aqueous nitric acid (30% by weight) were added with stirring. The aqueous phase was separated and the organic homogeneous phase was washed a further 3 times with 300 ml of water each time. Concentration of the organic phase resulted in a 50% by weight butanolic product solution, the predominant 2,4,6-tris (butoxycarbonylamino) -1,3,5-triazine (27.3 A%), 2-methoxycarbonylamino-4 , 6-bis (butoxycarbonylamino) -1,3,5-triazine (33.9 A%), 2,4-bis (butoxycarbonylamino) - 6-amino-1,3,5-triazine (6.9 A- %), 2,4-bis (methoxycarbonylamino) -6-butoxycarbonylamino-1,3,5-triazine (12.6 A%), 2-butoxycarbonylamino-4-methoxycarbonylamino-6-amino-1,3,5- triazine (4.9 A%) and tris (methoxycarbonylamino) -1,3,5-triazine (8.0 A%) contained (HPLC, ¹ H, ¹³ C NMR).

Claims (10)

Process for the preparation of alkoxycarbonylamino-triazines of the formula I.

in which Y ^{1 is} hydrogen, C ₁ -C ₄ alkyl, phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen or a radical of the formula NR ⁵ R ⁶ and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another are each hydrogen or a radical of the formula COOX or X, where X is C ₁ -C ₁₃ -alkyl, the carbon structure of which is interrupted by 1 or 2 oxygen atoms in ether function and / or by Hydroxy may be substituted, or C ₃ -C ₆ alkenyl, with the proviso that in formula I at least one of the radicals R ¹ to R ⁴ , or if Y ^{1 is} NR ⁵ R ⁶ , at least one of the radicals R ¹ to R ⁶ means COOX, by reacting a triazine of the formula II

in which Y ^{2 is} hydrogen, C ₁ -C ₄ -alkyl, amino or phenyl which is optionally substituted by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen, and R ¹ to R ⁴ each have the abovementioned meaning , with the proviso that in formula II, if Y ^{2 is} not amino, at least one of the radicals R ¹ to R ^{4 is} hydrogen, with carbonic acid esters in the presence of an alcohol and a base, characterized in that the triazine of the formula II with a cyclic carbonic acid ester of formula III

in which L is ethylene, 1,2- or 1,3-propylene or 1,2-, 1,4-2,3- or 1,3-butylene, and optionally with minor amounts of an acyclic carbonic acid ester of the formula IV Z ¹ O-CO-OZ ² (IV), in which Z ¹ and Z ² each independently represent C ₁ -C ₈ alkyl, and a C ₁ -C ₁₃ alkanol, the carbon structure of which can be interrupted by 1 or 2 oxygen atoms in ether function and / or substituted by hydroxy, or one C ₃ -C ₆ alkenol in the presence of an alkali or alkaline earth alkoxide as a base. A method according to claim 1, characterized in that one uses a C ₁ -C ₁₃ alkanol. A method according to claim 1, characterized in that an alkali alkanolate is used as the base. A method according to claim 1, characterized in that a cyclic carbonic acid ester of the formula III, in the L means ethylene or 1,2-propylene. A method according to claim 1, characterized in that one carries out the reaction at a temperature of 20 to 180 ° C. A method according to claim 1, characterized in that the reaction with 1 to 50 mol of alkanol, each based to one mole equivalent Amino groups in the triazine of the formula II. A method according to claim 1, characterized in that the reaction with 0.1 to 10 mol of cyclic carbonic acid ester, each based on one molar equivalent Amino groups in the triazine of the formula II. A method according to claim 1, characterized in that the reaction with 0.1 to 10 molar equivalents of alkali or alkaline earth alkoxide, each based on one molar equivalent Amino groups in the triazine of the formula II. A method according to claim 1, characterized in that you put that triazine II and alkanol and then in any Order of alkali or alkaline earth alkoxide, in the solid state and / or solved in alkanol and carbonic acid esters metered in, the metering of alkali or alkaline earth alkoxide and carbonic acid esters Completely before the start of the reaction or partly before the start of the reaction and partly can take place after the start of the reaction. A method according to claim 1, characterized in that 0 to 25 mol% of the cyclic carbonic acid esters of the formula III acyclic carbonic acid esters Formula IV can be replaced.